CN104294344A - Method for preparing nano/submicron/micron multi-stage anode alumina template - Google Patents
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- CN104294344A CN104294344A CN201410482892.3A CN201410482892A CN104294344A CN 104294344 A CN104294344 A CN 104294344A CN 201410482892 A CN201410482892 A CN 201410482892A CN 104294344 A CN104294344 A CN 104294344A
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Abstract
The invention discloses a method for preparing a nano/submicron/micron multi-stage anode alumina template. The method comprises the following steps: firstly, washing a high-purity aluminum sheet, and subsequently performing electrochemical polishing; performing anodic oxidation by using an oxalic acid-water-ethanol mixed solution as electrolyte, thereby obtaining a porous anode alumina membrane with an aluminum substrate; enabling a submicron structural unit to enter into a competitive growth mode by adjusting the conditions of voltage and the current density, thereby forming island-shaped and strip-shaped micro-grade structure unit clusters of different shapes; putting the alumina membrane with the aluminum substrate into a chromium trioxide and phosphoric acid mixing solution so as to remove the membrane, subsequently performing low-voltage anode oxidation in an oxalic acid solution, and performing hole expansion treatment by using a phosphoric acid solution, thereby obtaining the anode alumina template of a nano/submicron/micron multi-stage pore pipeline structure. The method has the advantages that the raw materials are easily available, the cost is low, the equipment is simple, the controllability is good, and the like, and the feasibility of industrial production is greatly improved.
Description
Technical field
The present invention relates to a kind of method preparing the multistage anodic oxidation aluminium formwork of nano/submicron/micron, be specifically related to the preparation method of the multistage anodic oxidation aluminium formwork of a kind of nano/submicron/micron.
Background technology
Nature also exists numerous natural nano/submicron/micron multistage composite structured material, and as the blade of lotus leaf surface, paddy rice, the skin etc. of shark, they are one of rich and varied natural important component parts as the functional materials that a class is important.At present, the nano/submicron/micron multistage composite structured material of synthetic is applied widely at numerous subjects such as super-hydrophobic, bionics and field because having various excellent specific property.The method preparing nano/submicron/micron multistage composite structured material is at present mainly direct synthesis technique and template, and direct synthesis technique of comparing, template is applied widely owing to having the advantages such as adjustability is good, of good reliability, reproducible.But the current multistage template of nano/submicron/micron is mainly derived from natural materials or photoetching preparation technology, there are starting material and be difficult to the shortcomings such as batch obtains, with high costs, instrument and supplies is complicated, these problems are never well solved.
It is anode that anodizing of aluminium process refers to aluminium, is placed in electrolyte solution and carries out energising process, utilizes electrolytic action to make its surface form the process of porous anodic alumina films.Except membrane process refer to alumilite process after remove prepared porous anodic alumina films and retain the process of aluminium substrate.Reaming procedure refers to and is immersed in reaming liquid by obtained porous anodic alumina films, utilizes the chemical milling of reaming liquid to be used for etch away parts zone of oxidation, thus makes the process that porous anodic alumina films hole increases.Anodizing of aluminium process and membrane removal, reaming procedure have the advantages such as technique is simple, repeatability is good, controllability is good, but application the method only can form the more shallow indenture of diameter within hundreds of nanometer on aluminium surface at present, therefore, be limited to prior art, anodizing of aluminium process and membrane removal, reaming procedure are not applied in the preparation technology of the multistage anodic oxidation aluminium formwork of nano/submicron/micron.
Summary of the invention
The present invention is directed to prior art starting material and be difficult to the shortcomings such as batch obtains, with high costs, instrument and supplies is complicated, the preparation method of the multistage anodic oxidation aluminium formwork of a kind of nano/submicron/micron is provided, the present invention utilizes anodizing of aluminium process and membrane removal, chambering process has come, have with low cost, technique is simple, the advantage such as reproducible.
The present invention adopts following technical scheme:
A preparation method for the multistage anodic oxidation aluminium formwork of nano/submicron/micron, comprises the steps:
High-purity aluminium flake is placed in dehydrated alcohol to step one successively and deionized water cleans, and obtains clean aluminium flake;
Step 2 is with clean aluminium flake for anode, and graphite is negative electrode, carries out constant voltage electrochemical etching, obtain the aluminium flake of polishing in perchloric acid and dehydrated alcohol mixing solutions;
Step 3 with the aluminium flake of polishing for anode, oxalic acid-water-ethanol mixing solutions be electrolytic solution to carry out anode oxidation process, anodizing temperature is 0 ~ 5 DEG C, obtains the porous anodic alumina films with aluminium substrate;
It is that the chromium trioxide of 55 ~ 85 DEG C and phosphoric acid mixed aqueous solution soak 8 ~ 12 hours that the porous anodic alumina films with aluminium substrate that step 3 obtains by step 4 is placed in temperature, clean with deionized water afterwards, obtain the aluminium flake that surface has the multistage indenture of submicron/micron;
The aluminium flake that the surface that step 4 obtains by step 5 has the multistage indenture of submicron/micron is anode, graphite is negative electrode, oxalic acid aqueous solution is that electrolytic solution is to carry out anodic oxidation, apply phosphate aqueous solution subsequently and expanding treatment is carried out to it, thus obtain the anodic oxidation aluminium formwork with nano/submicron/micron multi-stage porous pipeline configuration.
Massfraction >=99.99% of the high-purity aluminium flake of described step one.
In step 2, the voltage of described constant voltage electrochemical etching is 18 ~ 25V, and in described perchloric acid and dehydrated alcohol mixing solutions, the volume ratio of perchloric acid and dehydrated alcohol is 0.2 ~ 0.3:1, and polish temperature is 0 ~ 5 DEG C, and polishing time is 5 ~ 8 minutes.
In step 3, described anode oxidation process is specially: first adopt constant current density boosting, setting current density is 50 ~ 60mA/cm
2, when voltage rise enters the constant voltage anodic oxidation stage to during 495 ~ 605V appointment numerical value; When current density drops to 15 ~ 20mA/cm
2specify during numerical value and stop anodic oxidation.
In step 3, described oxalic acid-water-ethanol mixing solutions is the mixing solutions of oxalic acid aqueous solution and dehydrated alcohol; Oxalic acid aqueous solution and dehydrated alcohol are 1 ~ 20:1 by volume, and the concentration of oxalic acid aqueous solution is 0.28 ~ 0.32mol/L.
In step 4, in described chromium trioxide and phosphoric acid mixed aqueous solution, chromium trioxide and the weight percent shared by phosphoric acid are respectively 1.6 ~ 4.2% and 4.8 ~ 7.8%.
In step 5, the concentration of described oxalic acid aqueous solution is 0.28 ~ 0.32mol/L, and anodizing temperature is 2 ~ 5 DEG C, and anodic oxidation voltage is 30 ~ 50V, and anodizing time is 8 ~ 15 minutes.
In step 5, the mass percent concentration of described phosphate aqueous solution is 4 ~ 6%, and reaming temperature is 28 ~ 32 DEG C, and pore-enlargement is 5 ~ 20 minutes.
Beneficial effect of the present invention:
(1) the present invention prepares the anodic oxidation aluminium formwork with nano/submicron/micron multi-stage porous pipeline configuration by anodizing of aluminium process and membrane removal, reaming procedure, compare with the template prepared by natural material pattern and photolithography, it has, and starting material easily obtain, with low cost, equipment simple, be applicable to the advantages such as scale operation, substantially increase the feasibility that it is applied to production;
(2) the present invention can realize to nano/submicron/micron multi-stage porous pipeline configuration anodic oxidation aluminium formwork microtexture by carrying out simple adjustment to voltage, current density, electrolytic solution composition and pore-enlargement modulation, have easy to operate, technique is simple, the advantage such as of good reliability and reproducible;
(3) the present invention can prepare submicron and micrometer structure in a step anode oxidation process simultaneously, effectively simplifies preparation technology.
Accompanying drawing explanation
The voltage curve that Fig. 1 (a) ~ Fig. 1 (b) is alumilite process process in embodiment 1 and current density plot figure;
Fig. 2 is prepared porous anodic alumina films back side topography scan Electronic Speculum figure in embodiment 1;
Fig. 3 is the aluminium substrate surface topography scanning electron microscope (SEM) photograph in embodiment 1 after membrane removal process;
Fig. 4 is nano/submicron/micron multistage anodic oxidation aluminium formwork surface topography scanning electron microscope (SEM) photograph prepared in embodiment 1;
Fig. 5 is prepared porous anodic alumina films back side topography scan Electronic Speculum figure in embodiment 2;
Fig. 6 is nano/submicron/micron multistage anodic oxidation aluminium formwork surface topography scanning electron microscope (SEM) photograph prepared in embodiment 2.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment
A preparation method for the multistage anodic oxidation aluminium formwork of nano/submicron/micron, comprises the steps:
(1) high-purity aluminium flake of massfraction >=99.99% is placed in dehydrated alcohol successively and deionized water cleans, thus obtains clean aluminium flake;
(2) the clean aluminium flake obtained with step (1) is for anode, graphite is negative electrode, and at 0 DEG C, the volume ratio of perchloric acid and dehydrated alcohol is carry out constant voltage electrochemical etching in the mixing solutions of 0.2:1, and voltage is 18V, polishing time is 8 minutes, obtains the aluminium flake of polishing;
(3) aluminium flake of the polishing obtained with step (2) is for anode, graphite is negative electrode, the volume ratio of solution A (0.28mol/L oxalic acid aqueous solution) and solution B (dehydrated alcohol) be the mixing solutions of A:B=1:1 to carry out anode oxidation process, temperature is 0 DEG C; The voltage curve that Fig. 1 (a) ~ Fig. 1 (b) is alumilite process process in embodiment 1 and current density plot figure: as can be seen from Fig. 1 (a) ~ Fig. 1 (b), adopt constant current density boosting at the initial period of anode oxidation process, setting current density is 60mA/cm
2, now because aluminium flake surface can generate the aluminum oxide film of one deck densification, voltage can reach about 181V instantaneously, afterwards because compact aluminum oxide film changes porous alumina membrane into, makes the resistivity of film reduce thus make voltage quickly fall to about 163V; Subsequently, voltage starts to rise gradually with the carrying out of anode oxidation process, from Fig. 1, voltage curve can find out voltage in time in irregular ascendant trend, reflect that now anode oxidation process enters the competitive growth pattern of structural unit, under competitive growth pattern, the growth of structural unit is nonsynchronous, when voltage rise is to entering the constant voltage anodic oxidation stage during 605V; In the constant voltage anodic oxidation stage, current density declines gradually, when current density drops to 20mA/cm
2time stop anodic oxidation reactions obtaining with aluminium substrate porous anodic alumina films; Data in Fig. 1 (a) ~ Fig. 1 (b) obtain with the digital multimeter measurement that model is Keithley2010.In addition, under competitive growth pattern, the structural unit of dominant growth can occupy the growing space of adjacent structural units, numerous structural unit will form cluster-shaped projection jointly, thus forms rough appearance structure at prepared porous anodic alumina films (back side) near the side of aluminium substrate.Prepared porous anodic alumina films back side topography scan Electronic Speculum figure as shown in Figure 2, as can see from Figure 2, numerous submicron order structure unit constitutes micron-sized structural unit cluster, and in being separated island distribution, the surface-area of micron scale clusters is about tens of ~ hundreds of square micron.Fig. 2 obtained by following condition: first porous anodic alumina films prepared in embodiment 1 is carried out the process of sputtering metal spraying except after aluminium, is then that the field emission scanning electron microscope of LEO1530VP carries out test observation to the porous anodic alumina films back side and obtains by model.
(4) chromium trioxide (1.6%) and the immersion of phosphoric acid (7.8%) mixed aqueous solution that the porous anodic alumina films with aluminium substrate that step (3) obtains are placed in 55 DEG C carry out membrane removal process in 12 hours, clean with deionized water afterwards, obtain the aluminium substrate that surface has pit; After step (4) process, prepared porous anodic alumina films can be completely removed, and because its backside barrier layer place micron scale clusters is in being separated island distribution, therefore can leave micron order pit on aluminium substrate surface.Fig. 3 is the aluminium substrate surface topography scanning electron microscope (SEM) photograph in embodiment 1 after membrane removal process.As can see from Figure 3, prepared aluminium substrate surface spreads all over the large pit that surface-area is about tens of ~ hundreds of square micron, and these pits follow the structural unit cluster-shaped projection (as shown in Figure 2) at the prepared porous anodic alumina films back side in matched molds corresponding relation.Owing to bottom the structural unit of porous alumina membrane being the semisphere of shape at the bottom of test tube, aluminium substrate surface will be made after step (4) to be covered with the hemispherical small rut of submicron order, and the small rut of these submicron orders is about tens of ~ hundreds of square micron large pit with surface-area defines submicron/micron composite structure on the surface of aluminium substrate jointly.Fig. 3 obtained by following condition: the aluminium substrate first surface prepared in embodiment 1 with submicron/micron compound pit carries out the process of sputtering metal spraying, then carries out test observation with the field emission scanning electron microscope that model is LEO 1530 VP and obtains.
(5) surface obtained with step (4) has the aluminium substrate of submicron/micron compound pit for anode, graphite is negative electrode, 0.28mol/L oxalic acid aqueous solution be electrolytic solution to carry out anodic oxidation 8 minutes, anodic oxidation voltage is 40V, and temperature is 2 DEG C; Subsequently application quality percentage concentration be 4% phosphate aqueous solution expanding treatment is carried out to it, reaming temperature is 28 DEG C, and pore-enlargement is 20 minutes, finally obtains the multistage anodic oxidation aluminium formwork of nano/submicron/micron.Prepared nano/submicron/micron multistage anodic oxidation aluminium formwork surface topography scanning electron microscope (SEM) photograph as shown in Figure 4, as can see from Figure 4, after step (5) process, the aluminium substrate that surface has submicron/micron compound pit can produce numerous nano level hole in the bottom of submicron order pit, thus forms nano/submicron/micron multi-stage.The mean diameter of measuring result display nano level hole is about 45 nanometers, and the area of the large pit of micron order is about tens of ~ hundreds of square micron.Fig. 4 obtained by following condition: first the multistage anodic oxidation aluminium formwork of nano/submicron/micron prepared in embodiment 1 is carried out the process of sputtering metal spraying, then carry out test observation with the field emission scanning electron microscope that model is LEO1530VP and obtain.
Embodiment 2
A preparation method for the multistage anodic oxidation aluminium formwork of nano/submicron/micron, comprises the steps:
(1) high-purity aluminium flake of massfraction >=99.99% is placed in dehydrated alcohol successively and deionized water cleans, thus obtains clean aluminium flake;
(2) the clean aluminium flake obtained with step (1) is for anode, graphite is negative electrode, and at 5 DEG C, the volume ratio of perchloric acid and dehydrated alcohol is carry out constant voltage electrochemical etching in the mixing solutions of 0.3:1, and voltage is 25V, polishing time is 5 minutes, obtains the aluminium flake of polishing;
(3) aluminium flake of the polishing obtained with step (2) is for anode, graphite is negative electrode, the volume ratio of solution A (0.32mol/L oxalic acid aqueous solution) and solution B (dehydrated alcohol) is that the mixing solutions of A:B=20:1 is to carry out anode oxidation process, temperature is 5 DEG C: first adopt constant current density boosting, setting current density is 60mA/cm
2, when voltage rise is to entering the constant voltage anodic oxidation stage during 495V; When current density drops to 15mA/cm
2time stop anodic oxidation reactions obtaining with aluminium substrate porous anodic alumina films; Prepared porous anodic alumina films back side topography scan Electronic Speculum figure as shown in Figure 5, as can see from Figure 5, numerous submicron order structure unit constitutes micron-sized structural unit cluster, and distribute in ribbon, the surface-area of micron scale clusters is about tens of ~ hundreds of square micron.Fig. 5 obtained by following condition: first porous anodic alumina films prepared in embodiment 2 is carried out the process of sputtering metal spraying except after aluminium, is then that the field emission scanning electron microscope of LEO1530VP carries out test observation to the porous anodic alumina films back side and obtains by model.
(4) chromium trioxide (4.2%) and the immersion of phosphoric acid (4.8%) mixed aqueous solution that the porous anodic alumina films with aluminium substrate that step (3) obtains are placed in 85 DEG C carry out membrane removal process in 8 hours, clean with deionized water afterwards, obtain the aluminium substrate that surface has pit; After step (4) process, prepared porous anodic alumina films can be completely removed, and because its backside barrier layer place micron scale clusters is ribbon distribution, therefore can leave micron order pit on aluminium substrate surface.
(5) surface obtained with step (4) has the aluminium substrate of submicron/micron compound pit for anode, graphite is negative electrode, 0.32mol/L oxalic acid aqueous solution be electrolytic solution to carry out anodic oxidation 15 minutes, anodic oxidation voltage is 30V, and temperature is 5 DEG C; Subsequently application quality percentage concentration be 6% phosphate aqueous solution expanding treatment is carried out to it, reaming temperature is 32 DEG C, and pore-enlargement is 5 minutes, finally obtains the multistage anodic oxidation aluminium formwork of nano/submicron/micron.Prepared nano/submicron/micron multistage anodic oxidation aluminium formwork surface topography scanning electron microscope (SEM) photograph as shown in Figure 6, as can see from Figure 6, after step (5) process, the aluminium substrate that surface has submicron/micron compound pit can produce numerous nano level hole in the bottom of submicron order pit, thus forms nano/submicron/micron multi-stage.The mean diameter of measuring result display nano level hole is about 10 nanometers, and the area of the large pit of micron order is about tens of ~ hundreds of square micron.Fig. 6 obtained by following condition: first the multistage anodic oxidation aluminium formwork of nano/submicron/micron prepared in embodiment 2 is carried out the process of sputtering metal spraying, then carry out test observation with the field emission scanning electron microscope that model is LEO1530VP and obtain.
Embodiment 3
A preparation method for the multistage anodic oxidation aluminium formwork of nano/submicron/micron, comprises the steps:
(1) high-purity aluminium flake of massfraction >=99.99% is placed in dehydrated alcohol successively and deionized water cleans, thus obtains clean aluminium flake;
(2) the clean aluminium flake obtained with step (1) is for anode, graphite is negative electrode, and at 3 DEG C, the volume ratio of perchloric acid and dehydrated alcohol is carry out constant voltage electrochemical etching in the mixing solutions of 0.25:1, and voltage is 22V, polishing time is 6 minutes, obtains the aluminium flake of polishing;
(3) aluminium flake of the polishing obtained with step (2) is for anode, graphite is negative electrode, the volume ratio of solution A (0.30mol/L oxalic acid aqueous solution) and solution B (dehydrated alcohol) is that the mixing solutions of A:B=10:1 is to carry out anode oxidation process, temperature is 3 DEG C: first adopt constant current density boosting, setting current density is 50mA/cm
2, when voltage rise is to entering the constant voltage anodic oxidation stage during 550V; When current density drops to 18mA/cm
2time stop anodic oxidation reactions obtaining with aluminium substrate porous anodic alumina films;
(4) chromium trioxide (2.9%) and the immersion of phosphoric acid (6.5%) mixed aqueous solution that the porous anodic alumina films with aluminium substrate that step (3) obtains are placed in 70 DEG C carry out membrane removal process in 10 hours, clean with deionized water afterwards, obtain the aluminium substrate that surface has pit; After step (4) process, prepared porous anodic alumina films can be completely removed, and because its backside barrier layer place micron scale clusters is ribbon distribution, therefore can leave micron order pit on aluminium substrate surface.
(5) surface obtained with step (4) has the aluminium substrate of submicron/micron compound pit for anode, graphite is negative electrode, 0.30mol/L oxalic acid aqueous solution be electrolytic solution to carry out anodic oxidation 10 minutes, anodic oxidation voltage is 50V, and temperature is 3 DEG C; Subsequently application quality percentage concentration be 5% phosphate aqueous solution expanding treatment is carried out to it, reaming temperature is 30 DEG C, and pore-enlargement is 10 minutes, finally obtains the multistage anodic oxidation aluminium formwork of nano/submicron/micron.The mean diameter of measuring result display nano level hole is about 20 nanometers, and the area of the large pit of micron order is about tens of ~ hundreds of square micron.
Nature also exists numerous natural nano/submicron/micron multistage composite structured material, and as the blade of lotus leaf surface, paddy rice, the skin etc. of shark, they are one of rich and varied natural important component parts.At present, the nano/submicron/micron multistage composite structured material of synthetic is applied widely at numerous subjects such as super-hydrophobic, bionics and field because having various excellent specific property, has become one of study hotspot of functional materials research field.The method preparing nano/submicron/micron multistage composite structured material is at present mainly direct synthesis technique and template, and direct synthesis technique of comparing, template is applied widely owing to having the advantages such as adjustability is good, of good reliability, reproducible.But the current multistage template of nano/submicron/micron is mainly derived from natural materials or photoetching preparation technology, there are starting material and be difficult to the shortcomings such as batch obtains, with high costs, instrument and supplies is complicated, these problems are never well solved.
The present invention is directed to prior art starting material and be difficult to batch acquisition, with high costs, the deficiencies such as instrument and supplies is complicated, the preparation method of the multistage anodic oxidation aluminium formwork of a kind of nano/submicron/micron is provided, the present invention utilizes anodizing of aluminium process and membrane removal, chambering process has come, as can be seen from above three embodiments, the present invention can modulate the structural parameter of the multistage anodic oxidation aluminium formwork of prepared nano/submicron/micron by carrying out simple adjustment to processing condition, there is technique simple, with low cost, adjustability and the advantage such as reproducible.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a preparation method for the multistage anodic oxidation aluminium formwork of nano/submicron/micron, is characterized in that, comprise the steps:
High-purity aluminium flake is placed in dehydrated alcohol to step one successively and deionized water cleans, and obtains clean aluminium flake;
Step 2 is with clean aluminium flake for anode, and graphite is negative electrode, carries out constant voltage electrochemical etching, obtain the aluminium flake of polishing in perchloric acid and dehydrated alcohol mixing solutions;
Step 3 with the aluminium flake of polishing for anode, oxalic acid-water-ethanol mixing solutions be electrolytic solution to carry out anode oxidation process, anodizing temperature is 0 ~ 5 DEG C, obtains the porous anodic alumina films with aluminium substrate;
It is that the chromium trioxide of 55 ~ 85 DEG C and phosphoric acid mixed aqueous solution soak 8 ~ 12 hours that the porous anodic alumina films with aluminium substrate that step 3 obtains by step 4 is placed in temperature, clean with deionized water afterwards, obtain the aluminium flake that surface has the multistage indenture of submicron/micron;
The aluminium flake that the surface that step 4 obtains by step 5 has the multistage indenture of submicron/micron is anode, graphite is negative electrode, oxalic acid aqueous solution is that electrolytic solution is to carry out anodic oxidation, apply phosphate aqueous solution subsequently and expanding treatment is carried out to it, thus obtain the anodic oxidation aluminium formwork with nano/submicron/micron multi-stage porous pipeline configuration.
2. preparation method according to claim 1, is characterized in that, massfraction >=99.99% of the high-purity aluminium flake of described step one.
3. preparation method according to claim 1, it is characterized in that, in step 2, the voltage of described constant voltage electrochemical etching is 18 ~ 25V, in described perchloric acid and dehydrated alcohol mixing solutions, the volume ratio of perchloric acid and dehydrated alcohol is 0.2 ~ 0.3:1, polish temperature is 0 ~ 5 DEG C, and polishing time is 5 ~ 8 minutes.
4. preparation method according to claim 1, is characterized in that, in step 3, described anode oxidation process is specially: first adopt constant current density boosting, setting current density is 50 ~ 60mA/cm
2, when voltage rise enters the constant voltage anodic oxidation stage to during 495 ~ 605V appointment numerical value; When current density drops to 15 ~ 20mA/cm
2specify during numerical value and stop anodic oxidation.
5. preparation method according to claim 1, is characterized in that, in step 3, described oxalic acid-water-ethanol mixing solutions is the mixing solutions of oxalic acid aqueous solution and dehydrated alcohol; Oxalic acid aqueous solution and dehydrated alcohol are 1 ~ 20:1 by volume, and the concentration of oxalic acid aqueous solution is 0.28 ~ 0.32mol/L.
6. preparation method according to claim 1, is characterized in that, in step 4, in described chromium trioxide and phosphoric acid mixed aqueous solution, chromium trioxide and the weight percent shared by phosphoric acid are respectively 1.6 ~ 4.2% and 4.8 ~ 7.8%.
7. preparation method according to claim 1, is characterized in that, in step 5, the concentration of described oxalic acid aqueous solution is 0.28 ~ 0.32mol/L, and anodizing temperature is 2 ~ 5 DEG C, and anodic oxidation voltage is 30 ~ 50V, and anodizing time is 8 ~ 15 minutes.
8. preparation method according to claim 1, is characterized in that, in step 5, the mass percent concentration of described phosphate aqueous solution is 4 ~ 6%, and reaming temperature is 28 ~ 32 DEG C, and pore-enlargement is 5 ~ 20 minutes.
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| CN104928746A (en) * | 2015-06-23 | 2015-09-23 | 华南理工大学 | Method for producing micro-surface three-dimensional interconnected-nanopore anodic aluminum oxide template |
| CN105297106A (en) * | 2015-10-26 | 2016-02-03 | 华南理工大学 | Method for preparing large-hole-interval porous anodic alumina membrane at high voltage |
| CN105401202A (en) * | 2015-10-26 | 2016-03-16 | 华南理工大学 | Method for coloring aluminum surface |
| CN107275204A (en) * | 2017-06-20 | 2017-10-20 | 华中科技大学 | A kind of nano photoelectric device preparation method based on porous anodic alumina template |
| CN110241450A (en) * | 2019-07-19 | 2019-09-17 | 广东工业大学 | A kind of porous anodic alumina template and its preparation method and application |
| CN113529150A (en) * | 2021-06-23 | 2021-10-22 | 华南理工大学 | Submicron alumina tube and preparation method and application thereof |
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| CN104928746A (en) * | 2015-06-23 | 2015-09-23 | 华南理工大学 | Method for producing micro-surface three-dimensional interconnected-nanopore anodic aluminum oxide template |
| CN104928746B (en) * | 2015-06-23 | 2017-06-06 | 华南理工大学 | A kind of method for preparing the three-dimensional interconnection nano-pore anodic oxidation aluminium formwork of micro- curved surface |
| CN105297106A (en) * | 2015-10-26 | 2016-02-03 | 华南理工大学 | Method for preparing large-hole-interval porous anodic alumina membrane at high voltage |
| CN105401202A (en) * | 2015-10-26 | 2016-03-16 | 华南理工大学 | Method for coloring aluminum surface |
| CN107275204A (en) * | 2017-06-20 | 2017-10-20 | 华中科技大学 | A kind of nano photoelectric device preparation method based on porous anodic alumina template |
| CN107275204B (en) * | 2017-06-20 | 2019-06-28 | 华中科技大学 | A kind of nano photoelectric device preparation method based on porous anodic alumina template |
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| CN113529150A (en) * | 2021-06-23 | 2021-10-22 | 华南理工大学 | Submicron alumina tube and preparation method and application thereof |
| CN113529150B (en) * | 2021-06-23 | 2022-03-29 | 华南理工大学 | Submicron alumina tube and preparation method and application thereof |
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